EP0037015A2 - Process for the preparation of 2-chloro-acetoacetic acid esters - Google Patents
Process for the preparation of 2-chloro-acetoacetic acid esters Download PDFInfo
- Publication number
- EP0037015A2 EP0037015A2 EP81102029A EP81102029A EP0037015A2 EP 0037015 A2 EP0037015 A2 EP 0037015A2 EP 81102029 A EP81102029 A EP 81102029A EP 81102029 A EP81102029 A EP 81102029A EP 0037015 A2 EP0037015 A2 EP 0037015A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- chloride
- temperatures
- chloroacetoacetic
- acid esters
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 9
- VCBFAUSKNYAKJZ-UHFFFAOYSA-N 2-chloro-3-oxobutanoic acid Chemical class CC(=O)C(Cl)C(O)=O VCBFAUSKNYAKJZ-UHFFFAOYSA-N 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 4
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000460 chlorine Substances 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 150000002148 esters Chemical class 0.000 claims abstract description 6
- WNVYZJSJUQUVSZ-UHFFFAOYSA-N 2-chloro-3-oxobutanoyl chloride Chemical compound CC(=O)C(Cl)C(Cl)=O WNVYZJSJUQUVSZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 5
- AXWKFRWLYPZEFQ-UHFFFAOYSA-N 3-oxobutanoyl chloride Chemical compound CC(=O)CC(Cl)=O AXWKFRWLYPZEFQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 4
- 150000001298 alcohols Chemical class 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- 239000000543 intermediate Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical class CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- -1 aliphatic alcohols Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- CCGSUNCLSOWKJO-UHFFFAOYSA-N cimetidine Chemical compound N#CNC(=N/C)\NCCSCC1=NC=N[C]1C CCGSUNCLSOWKJO-UHFFFAOYSA-N 0.000 description 1
- 229960001380 cimetidine Drugs 0.000 description 1
- RDULEYWUGKOCMR-UHFFFAOYSA-N ethyl 2-chloro-3-oxobutanoate Chemical compound CCOC(=O)C(Cl)C(C)=O RDULEYWUGKOCMR-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/46—Preparation of carboxylic acid esters from ketenes or polyketenes
Definitions
- the present invention relates to a process for the preparation of 2-chloroacetoacetic acid esters.
- 2-Chloroacetoacetic acid esters can be used for the preparation of coumaric acid derivatives, which are known as an intermediate for the production of crop protection agents.
- 2-chloroacetoacetic acid esters are also intermediates for pharmaceutical preparations, e.g. Cimetidine.
- the chlorination with sulfuryl chloride proceeds up to high conversions with a good yield (93-97%), but has the disadvantage that the gases generated during the reaction, S0 2 and HCl, have to be separated and the sulfur dioxide in again in a special work process the sulfuryl chloride must be converted.
- the aim of the present invention is a simple, powerful method. According to the invention, this is achieved by starting from diketene, this at temperatures from +10 to -40 ° C in the presence of chlorinated aliphatic hydrocarbon preferably with 1 to 3 carbon atoms as a solvent with HC1 in the acetoacetic acid chloride, by introducing chlorine at temperatures of ⁇ 10 to -40 ° C forms the 2-chloroacetoacetic acid chloride and the latter converted into the corresponding ester by adding preferably aliphatic alcohols having 1 to 4 carbon atoms.
- the chlorination can be carried out in the presence of acidic catalysts such as Lewis acids, for example PC1 3 , FeC1 3 , inorganic acids, for example sulfuric acid, perchloric acid, or strong organic carboxylic acids, for example acetic acid, trifluoroacetic acid, p-toluenesulfonic acid.
- acidic catalysts such as Lewis acids, for example PC1 3 , FeC1 3 , inorganic acids, for example sulfuric acid, perchloric acid, or strong organic carboxylic acids, for example acetic acid, trifluoroacetic acid, p-toluenesulfonic acid.
- Chlorinated aliphatic hydrocarbons such as carbon tetrachloride, ethyl chloride, dichloroethane, etc., preferably methylene chloride, are used as solvents.
- solvents such as carbon tetrachloride, ethyl chloride, dichloroethane, etc., preferably methylene chloride.
- 200 to 1000 g of solvent are used per mole of diketene.
- the molar ratio of HC1 to diketene in the first stage can vary widely, expediently 1.1 to 10 mol, preferably 1.95 to 6.5 mol, of HCl are used per mol of diketene.
- 0.9 to 1.1 moles of chlorine are preferably used per mole of acetoacetic acid chloride.
- the 2-chloroacetoacetic acid chloride obtained in the second stage is reacted with the appropriate alcohol with 1 to 4 carbon atoms implemented in a third stage.
- alcohols are methyl, ethyl, propyl, butyl alcohol.
- the amount of alcohol to be added is the stoichiometric amount. In some cases it may be appropriate to use a slight excess, advantageously from 0.1 to 0.3 mol.
- a particularly preferred embodiment of the invention consists in that the three stages can be carried out in the same reaction medium and reaction vessel without having to isolate one of the intermediates.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von 2-Chloracetessigsäureestern. 2-Chloracetessigsäureester können zur Herstellung von Cumarilsäurederivaten verwendet werden, die als Zwischenprodukt zur Herstellung von Pflanzenschutzmitteln bekannt sind. 2-Chloracetessigsäureester stellen auch Zwischenprodukte für pharmazeutische Präparate, z.B. Cimetidin, dar.The present invention relates to a process for the preparation of 2-chloroacetoacetic acid esters. 2-Chloroacetoacetic acid esters can be used for the preparation of coumaric acid derivatives, which are known as an intermediate for the production of crop protection agents. 2-chloroacetoacetic acid esters are also intermediates for pharmaceutical preparations, e.g. Cimetidine.
Bei den bisher bekannten Herstellungsverfahren wird von Acetessigsäureestern ausgegangen, die entweder mit Sulfurylchlorid oder mit Chlor chloriert werden.The previously known production processes are based on acetoacetic acid esters, which are chlorinated either with sulfuryl chloride or with chlorine.
Die Chlorierung mit Sulfurylchlorid verläuft zwar bis zu hohen Umsätzen mit guter Ausbeute (93-97%), hat jedoch den Nachteil, dass die bei der Reaktion entstehenden Gase, S02 und HCl, getrennt werden müssen und das Schwefeldioxid in einem speziellen Arbeitsprozess wieder in das Sulfurylchlorid umgewandelt werden muss.The chlorination with sulfuryl chloride proceeds up to high conversions with a good yield (93-97%), but has the disadvantage that the gases generated during the reaction, S0 2 and HCl, have to be separated and the sulfur dioxide in again in a special work process the sulfuryl chloride must be converted.
Bei der Chlorierung von Acetessigestern mit Chlor können, wenn die Reaktion kontinuierlich durchgeführt wird, relativ gute Selektivitäten und Ausbeuten erreicht werden (DE-OS 27 09 138).In the chlorination of acetoacetic esters with chlorine, if the reaction is carried out continuously, relatively good selectivities and yields can be achieved (DE-OS 27 09 138).
Ziel der vorliegenden Erfindung ist ein einfaches, leistungsfähiges Verfahren. Erfindungsgemäss wird dies dadurch erreicht, dass man von Diketen ausgeht, dieses bei Temperaturen von +10 bis -40°C in Gegenwart von chloriertem aliphatischen Kohlenwasserstoff vorzugsweise mit 1 bis 3 Kohlenstoffatomen als Lösungsmittel mit HC1 in das Acetessigsäurechlorid überführt, durch Einleiten von Chlor bei Temperaturen von ±10 bis -40°C das 2-Chloracetessigsäurechlorid bildet und letzteres durch Zugabe von vorzugsweise aliphatischen Alkoholen mit 1 bis 4 C-Atomen in den entsprechenden Ester überführt.The aim of the present invention is a simple, powerful method. According to the invention, this is achieved by starting from diketene, this at temperatures from +10 to -40 ° C in the presence of chlorinated aliphatic hydrocarbon preferably with 1 to 3 carbon atoms as a solvent with HC1 in the acetoacetic acid chloride, by introducing chlorine at temperatures of ± 10 to -40 ° C forms the 2-chloroacetoacetic acid chloride and the latter converted into the corresponding ester by adding preferably aliphatic alcohols having 1 to 4 carbon atoms.
Die Chlorierung kann in Gegenwart von sauren Katalysatoren, wie Lewis-Säuren, z.B. PC13, FeC13, anorganischen Säuren, z.B. Schwefelsäure, Perchlorsäure, oder starken organischen Carbonsäuren, z.B. Essigsäure, Trifluoressigsäure, p-Toluolsulfonsäure, durchgeführt werden. Diese Säuren werden in katalytischen Mengen, zweckmässig 0,1 bis 20 Mol%, bezogen auf eingesetztes Diketen, zugesetzt.The chlorination can be carried out in the presence of acidic catalysts such as Lewis acids, for example PC1 3 , FeC1 3 , inorganic acids, for example sulfuric acid, perchloric acid, or strong organic carboxylic acids, for example acetic acid, trifluoroacetic acid, p-toluenesulfonic acid. These acids are added in catalytic amounts, advantageously 0.1 to 20 mol%, based on the diketene used.
Als Lösungsmittel werden chlorierte aliphatische Kohlenwasserstoffe, wie Tetrachlorkohlenstoff, Aethylchlorid, Dichloräthan usw., vorzugsweise Methylenchlorid, verwendet. Zweckmässig setzt man pro Mol Diketen 200 bis 1000'g Lösungsmittel ein.Chlorinated aliphatic hydrocarbons such as carbon tetrachloride, ethyl chloride, dichloroethane, etc., preferably methylene chloride, are used as solvents. Appropriately, 200 to 1000 g of solvent are used per mole of diketene.
Das Molverhältnis HC1 zu Diketen in der ersten Stufe kann stark variieren, zweckmässig wird pro Mol Diketen 1,1 bis 10 Mol, vorzugsweise 1,95 bis 6,5 Mol HCl, angewendet.The molar ratio of HC1 to diketene in the first stage can vary widely, expediently 1.1 to 10 mol, preferably 1.95 to 6.5 mol, of HCl are used per mol of diketene.
Für die Chlorierung mit Chlor in der zweiten Stufe werden vorzugsweise pro Mol Acetessigsäurechlorid 0,9 bis 1,1 Mol Chlor angewendet.For chlorination with chlorine in the second stage, 0.9 to 1.1 moles of chlorine are preferably used per mole of acetoacetic acid chloride.
Zur Herstellung der gewünschten Ester wird das in der zweiten Stufe erhaltene 2-Chloracetessigsäurechlorid mit dem entsprechenden Alkohol mit 1 bis 4 C-Atomen in einer dritten Stufe umgesetzt. Solche Alkohole sind Methyl-, Aethyl-, Propyl-, Butylalkohol.To produce the desired esters, the 2-chloroacetoacetic acid chloride obtained in the second stage is reacted with the appropriate alcohol with 1 to 4 carbon atoms implemented in a third stage. Such alcohols are methyl, ethyl, propyl, butyl alcohol.
Die hinzuzusetzende Menge an Alkohol sind die stöchiometrischen Mengen. Es kann in manchen Fällen zweckmässig sein, einen leichten Ueberschuss, zweckmässig von 0,1 bis 0,3 Mol, anzuwenden.The amount of alcohol to be added is the stoichiometric amount. In some cases it may be appropriate to use a slight excess, advantageously from 0.1 to 0.3 mol.
Eine besonders bevorzugte Ausführungsform der Erfindung besteht darin, dass man die drei Stufen im selben Reaktionsmedium und Reaktionsgefäss, ohne dass eines der Zwischenprodukte isoliert werden muss, durchführen kann.A particularly preferred embodiment of the invention consists in that the three stages can be carried out in the same reaction medium and reaction vessel without having to isolate one of the intermediates.
In einem Doppelmantelkolben von 500 ml Grösse, ausgestattet mit Pressluftrührer, Thermometer, Gaseinleitungsrohr mit Fritte, Rückflusskühler und Kryomat, wurden 50,45 g (0,6 Mol) Diketen in 300 ml Methylenchlorid gelöst und auf -20oC abgekühlt. Nach Zusatz von 0,11 Mol% H2S04, bezogen auf Diketen, und 43,8 g (1,2 Mol) Chlorwasserstoff, bezogen auf Diketen, wurden nach 3 1/2 Stunden Rühren während 35 Minuten 42,5 g (0,6 Mol) Chlor eingeleitet und weitere 30 Minuten gerührt. Anschliessend wurde immer noch bei -20 bis -10°C 27,6 g (0,6 Mol) absoluter Aethanol zugetropft und während 15 Minuten gerührt.Equipped with Pressluftrührer, thermometer, gas inlet tube with frit, reflux condenser and Kryomat in a jacketed flask of 500 ml size, 50.45 g (0.6 mol) of diketene were dissolved in 300 ml of methylene chloride and cooled to -20 ° C. After adding 0.11 mol% of H 2 SO 4 , based on diketene, and 43.8 g (1.2 mol) of hydrogen chloride, based on diketene, 42.5 g (after 35 minutes stirring) were added for 35 minutes. 0.6 mol) chlorine introduced and stirred for a further 30 minutes. Subsequently, 27.6 g (0.6 mol) of absolute ethanol were still added dropwise at -20 to -10 ° C. and the mixture was stirred for 15 minutes.
Anschliessend wurde das-Lösungsmittel am Rotavap abgedampft. Es resultierten 98,7 g 2-Chloracetessigsäure- äthylester mit einem Gehalt von 83,4 Gew.%.The solvent was then evaporated off on a Rotavap. The result was 98.7 g of ethyl 2-chloroacetoacetate with a content of 83.4% by weight.
Nachstehende Tabelle zeigt die Ergebnisse weiterer Versuche.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT81102029T ATE3852T1 (en) | 1980-04-02 | 1981-03-18 | PROCESS FOR THE PREPARATION OF 2CHLORACETETTINE[UREESTERS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH2606/80 | 1980-04-02 | ||
| CH260680 | 1980-04-02 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0037015A2 true EP0037015A2 (en) | 1981-10-07 |
| EP0037015A3 EP0037015A3 (en) | 1981-12-30 |
| EP0037015B1 EP0037015B1 (en) | 1983-06-22 |
Family
ID=4237538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81102029A Expired EP0037015B1 (en) | 1980-04-02 | 1981-03-18 | Process for the preparation of 2-chloro-acetoacetic acid esters |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0037015B1 (en) |
| JP (1) | JPS56154438A (en) |
| AT (1) | ATE3852T1 (en) |
| CS (1) | CS217995B2 (en) |
| DD (1) | DD157794A5 (en) |
| DE (1) | DE3160460D1 (en) |
| IN (1) | IN151753B (en) |
| MX (1) | MX152284A (en) |
| PL (1) | PL134443B1 (en) |
| SU (1) | SU988187A3 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0061657A1 (en) * | 1981-03-26 | 1982-10-06 | Lonza Ag | Process for the preparation of 2-chloracetoacetamides |
| US8859786B2 (en) | 2011-04-01 | 2014-10-14 | Lonza Ltd | Preparation of 3,5-dioxo hexanoate ester in two steps |
| WO2017093214A1 (en) | 2015-12-03 | 2017-06-08 | Bayer Cropscience Aktiengesellschaft | Mesoionic halogenated 3-(acetyl)-1-[(1,3-thiazol-5-yl)methyl]-1h-imidazo[1,2-a]pyridin-4-ium-2-olate derivatives and related compounds as insecticides |
| WO2018229202A1 (en) | 2017-06-16 | 2018-12-20 | Basf Se | Mesoionic imidazolium compounds and derivatives for combating animal pests |
| CN109503381A (en) * | 2018-12-12 | 2019-03-22 | 安徽金禾实业股份有限公司 | 4- chloroacetyl acetacetic ester microchannel plate induction method and device |
| CN113877504A (en) * | 2021-11-03 | 2022-01-04 | 江苏恒安化工有限公司 | Preparation device and method of ethyl 4-chloroacetoacetate |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6025955A (en) * | 1983-07-22 | 1985-02-08 | Nippon Synthetic Chem Ind Co Ltd:The | Production of gamma-chloroacetoacetic acid ester |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2209683A (en) * | 1936-06-27 | 1940-07-30 | Carbide & Carbon Chem Corp | Halogenation of diketene |
| US3666793A (en) * | 1968-04-24 | 1972-05-30 | Lonza Ag | Process for the production of {65 -chloroacetoacetic acid esters |
| JPS51113824A (en) * | 1975-03-27 | 1976-10-07 | Nippon Synthetic Chem Ind Co Ltd:The | Preparation of gamma-chloroacetoacetyl chloride |
-
1981
- 1981-03-12 IN IN271/CAL/81A patent/IN151753B/en unknown
- 1981-03-18 EP EP81102029A patent/EP0037015B1/en not_active Expired
- 1981-03-18 DE DE8181102029T patent/DE3160460D1/en not_active Expired
- 1981-03-18 AT AT81102029T patent/ATE3852T1/en not_active IP Right Cessation
- 1981-03-26 PL PL1981230340A patent/PL134443B1/en unknown
- 1981-03-30 SU SU813262355A patent/SU988187A3/en active
- 1981-03-30 CS CS812363A patent/CS217995B2/en unknown
- 1981-03-31 DD DD81228780A patent/DD157794A5/en unknown
- 1981-04-01 JP JP4924781A patent/JPS56154438A/en active Granted
- 1981-04-02 MX MX186693A patent/MX152284A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2209683A (en) * | 1936-06-27 | 1940-07-30 | Carbide & Carbon Chem Corp | Halogenation of diketene |
| US3666793A (en) * | 1968-04-24 | 1972-05-30 | Lonza Ag | Process for the production of {65 -chloroacetoacetic acid esters |
| JPS51113824A (en) * | 1975-03-27 | 1976-10-07 | Nippon Synthetic Chem Ind Co Ltd:The | Preparation of gamma-chloroacetoacetyl chloride |
Non-Patent Citations (4)
| Title |
|---|
| CHEMICAL ABSTRACTS, Band 34, Nr. 18, 20-09-1940, spalte 62228 Columbus, Ohio, US C.D. HURD et al.: "Chlorination and Structure of Acetylketene" & J. Am. Chem. Soc. 62, 1147-8 (1940) * insgesamt * * |
| CHEMICAL ABSTRACTS, Band 46, Nr. 17, 10-09-1952, spalte 8115c Columbus, Ohio, US V.V. PEREKALIN et al.: "Reactions of Diketene. Reaction of Diketene with some Weakly Basic Aromatic Amines" & Zhur. Obshchei. Khim. 21, 1995-2001 (1951) * insgesamt * * |
| CHEMICAL ABSTRACTS, Band 86, Nr. 19. 09-05-1977, seite 506, Zusammenfassung 139408h Columbus, Ohio, US & JP-A-51 113 824 (Nippon Synthetic Chemical Industry) (27-03-1975) * insgesamt * * |
| Chemische Berichte, Band 81, Nr. 5 Oktober 1948, Berlin, DE H. BRINTZINGER et al.: "Notiz Uber Thioketone", seiten 380,381 * Insgesamt * * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0061657A1 (en) * | 1981-03-26 | 1982-10-06 | Lonza Ag | Process for the preparation of 2-chloracetoacetamides |
| US4801750A (en) * | 1981-03-26 | 1989-01-31 | Lonza Ltd. | Process for the produciton of 2-chloroacetoacetic acid amides |
| US8859786B2 (en) | 2011-04-01 | 2014-10-14 | Lonza Ltd | Preparation of 3,5-dioxo hexanoate ester in two steps |
| US9296718B2 (en) | 2011-04-01 | 2016-03-29 | Lonza Ltd | Preparation of 3,5-dioxo hexanoate ester in two steps |
| WO2017093214A1 (en) | 2015-12-03 | 2017-06-08 | Bayer Cropscience Aktiengesellschaft | Mesoionic halogenated 3-(acetyl)-1-[(1,3-thiazol-5-yl)methyl]-1h-imidazo[1,2-a]pyridin-4-ium-2-olate derivatives and related compounds as insecticides |
| WO2018229202A1 (en) | 2017-06-16 | 2018-12-20 | Basf Se | Mesoionic imidazolium compounds and derivatives for combating animal pests |
| CN109503381A (en) * | 2018-12-12 | 2019-03-22 | 安徽金禾实业股份有限公司 | 4- chloroacetyl acetacetic ester microchannel plate induction method and device |
| CN109503381B (en) * | 2018-12-12 | 2022-04-29 | 安徽金禾实业股份有限公司 | 4-chloroacetoacetic acid ethyl ester microchannel reaction method and device |
| CN113877504A (en) * | 2021-11-03 | 2022-01-04 | 江苏恒安化工有限公司 | Preparation device and method of ethyl 4-chloroacetoacetate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56154438A (en) | 1981-11-30 |
| EP0037015B1 (en) | 1983-06-22 |
| SU988187A3 (en) | 1983-01-07 |
| DE3160460D1 (en) | 1983-07-28 |
| MX152284A (en) | 1985-06-20 |
| DD157794A5 (en) | 1982-12-08 |
| PL134443B1 (en) | 1985-08-31 |
| IN151753B (en) | 1983-07-23 |
| ATE3852T1 (en) | 1983-07-15 |
| PL230340A1 (en) | 1981-11-27 |
| JPH0125735B2 (en) | 1989-05-19 |
| EP0037015A3 (en) | 1981-12-30 |
| CS217995B2 (en) | 1983-02-25 |
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